EP2956569B1 - Procédé permettant le revêtement de surfaces métalliques pour éviter la formation de piqûres sur des surfaces métalliques contenant du zinc - Google Patents

Procédé permettant le revêtement de surfaces métalliques pour éviter la formation de piqûres sur des surfaces métalliques contenant du zinc Download PDF

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EP2956569B1
EP2956569B1 EP14703815.2A EP14703815A EP2956569B1 EP 2956569 B1 EP2956569 B1 EP 2956569B1 EP 14703815 A EP14703815 A EP 14703815A EP 2956569 B1 EP2956569 B1 EP 2956569B1
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Prior art keywords
silane
aqueous
composition
cleaning
additive according
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German (de)
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EP2956569A1 (fr
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Martin Mrochem
Jürgen SPECHT
Hardy Wietzoreck
Olaf Dahlenburg
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Chemetall GmbH
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Chemetall GmbH
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78Pretreatment of the material to be coated
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes
    • C09D183/08Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3742Nitrogen containing silicones
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/361Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78Pretreatment of the material to be coated
    • C23C22/80Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/20Other heavy metals
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20Use of solutions containing silanes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31652Of asbestos
    • Y10T428/31663As siloxane, silicone or silane

Definitions

  • the present application relates to methods for coating metallic surfaces to prevent specks on zinc-containing metallic surfaces using a silane additive in an aqueous cleaning composition, in an aqueous rinse liquid and / or in an aqueous activation composition.
  • Stipes are white or bright spots on the metal surface that look like a crater under the microscope. In crass situations, the crater-shaped pebbles can even protrude about 1 mm high from the metallic surface, the zinc-containing coating, for example, a hot-dip galvanizing inside the crater-shaped lip more or less dissolved.
  • FIG. 1 shows a particularly large bar in the scanning electron micrograph on a galvanized and then zinc-phosphated metallic surface, which protrudes about 1 mm high from the coated surface and in the interior of which the galvanization is largely resolved. Staining may be the starting point for more damage from corrosion as the protective zinc or zinc alloy layer is severely damaged at the lip and may be the starting point for more damage from delamination of the overlying coating. Therefore, a single stem disturbs already, and therefore specks in industrial practice are to be avoided altogether.
  • the reworking is done in particular by the fact that these parts in the area around the damaged area, for example, by grinding or sandblasting and possibly processed to the metallic surface and then again be compensated eg by aftertreatment such as by phosphating and with one or more coats. Due to the fact that such repairs often occur in a line of body coating in the automotive industry and are usually performed by hand, the time and effort is very high.
  • Stippings are often recognized only at the end of a treatment line after the conversion coating or even after the further coating with an electrodeposition paint, powder coating or primer or palpated with the hands as bumps. Only under certain conditions may larger specks on cleaned metallic surfaces, on rinsed metallic surfaces, on activated metallic surfaces, or on conversion coated e.g. phosphated metallic surfaces are detected when the treated substrates are removed from the bath.
  • a typical treatment line for phosphating may include at least one cleaning zone with an aqueous cleaning composition, at least one rinse zone with an aqueous rinse, and optionally at least one pretreatment zone prior to phosphating with an aqueous activation composition A) or B), and then zones for phosphating and comprise at least one new rinse with an aqueous rinse liquid, optionally before at least one zone for at least one finish.
  • Another typical treatment line may be, for example, at least one cleaning zone with an aqueous cleaning composition, at least one rinse zone with an aqueous rinse and at least one zone for the treatment or pretreatment with a silane-containing conversion conversion aqueous composition and optionally thereafter at least one rinse zone with an aqueous rinse and optionally also include zones for at least one coating.
  • a typical treatment line may include, for example, at least one cleaning zone with an aqueous cleaning composition, at least one rinse zone with an aqueous rinse liquid, and at least one zone for treatment or pretreatment with an aqueous composition for conversion coating and optionally thereafter at least one rinse zone with an aqueous rinse liquid and optionally at least include a zone for at least one finish.
  • a zone is in practice equivalent to a level.
  • EP 0 224 190 A2 describes methods of activating metal surfaces between the purge / purge and zinc phosphating steps using aqueous alkaline solutions containing titanium ions and phosphate ions in which the activating solutions are adjusted to a pH of 8 to 10 and additionally disodium tetraborate and / or others soluble alkali or alkaline earth metal borates added.
  • EP 0 264 151 A1 discloses processes for producing phosphate coatings on steel and galvanized steel composite parts by alkaline cleaning, rinsing with aqueous rinse and zinc phosphating, in which the cleaned composite parts are rinsed with a rinse bath containing at least 0.2 g / L alkali borate, at least 0.1 g / L contains alkali silicate and at least 0.05 g / L alkali nitrite.
  • DE 102008054407 A1 teaches methods of phosphating metallic surfaces wherein the metallic surfaces are treated with an aqueous colloidal phosphating agent and titanium prior to phosphating and wherein the activating agent contains at least one water-soluble silicon compound having at least one organic group.
  • aqueous cleaning composition When metallic surfaces are to be coated and not recently hot-dip galvanized, it is common practice to first clean, especially degrease, the metallic surfaces in an aqueous cleaning composition.
  • an acidic, neutral, alkaline or strongly alkaline cleaning composition it is possible in particular to use an acidic, neutral, alkaline or strongly alkaline cleaning composition, but optionally also an acid pickling composition.
  • the aqueous cleaning composition may contain, in addition to at least one surfactant, optionally also a scaffold or / and other additives such as e.g. Complexing agent included.
  • the water optionally also containing an additive dissolved in water, such as e.g. a nitrite may be added.
  • a phosphating phosphating solution which may be followed by activation, may contain in addition to the cations and in addition to a content of orthophosphate, in particular a content of condensed phosphate, nitrate, fluoride, complex fluoride, organic Polymer and / or accelerator such as accelerators based on nitrite, chlorate, peroxide or / and nitro compound such as nitroguanidine included.
  • aqueous phosphating solutions e.g. Zinc manganese nickel phosphating solutions
  • silane-containing solutions contain, in addition to at least one silane, silanol or / and siloxane, optionally also an addition of organic polymer / copolymer, cations, fluoride, complex fluoride, silicate or / and other additives such.
  • the treatment or pretreatment with a conversion composition may be followed, if necessary, by a rinsing with water followed by a treatment with a rinsing solution, which may optionally be followed by rinsing with water.
  • the first lacquer layer after a pretreatment is an electrodeposition coating with an electrodeposition paint such as e.g. a cathodic electrodeposition paint (KTL, e-coat), a primer or a powder coating used.
  • the object is achieved by using a silane additive to prevent specks on zinc-containing metallic surfaces 1.) in an aqueous cleaning composition, 2.) in an aqueous rinsing liquid, the a) before cleaning, the b) in the middle of several cleaning zones, c) immediately after cleaning and / or d) used as a liquid for cooling, or / and 3.) in an aqueous activating composition, the content of each of at least one silane, silanol or / and siloxane in at least one of these aqueous Compositions in the range of 0.001 to 5 g / L calculated on the particular silane.
  • the silane is referred to herein as the starting compound of the reaction chain, e.g. from silane via silanol to siloxane.
  • silane or “silane additive” includes silane, silanol or / and siloxane - as will be explained in more detail below.
  • the panels were first cleaned with an aqueous cleaning liquid Gardoclean ® 854/5 Chemetall GmbH at a pH value of 10.5 by dipping at 60 ° C for 10 minutes and immediately thereafter rinsed with tap water for 30 seconds by immersion at room temperature. Activation was carried out thereto subsequently with an aqueous activating composition A), with 3 g / L activating concentrate Gardolene ® V 6559 from Chemetall GmbH had been added in liquid form to deionized water before, with stirring.
  • Gardoclean ® 854/5 Chemetall GmbH at a pH value of 10.5 by dipping at 60 ° C for 10 minutes and immediately thereafter rinsed with tap water for 30 seconds by immersion at room temperature.
  • Activation was carried out thereto subsequently with an aqueous activating composition A), with 3 g / L activating concentrate Gardolene ® V 6559 from Chemetall GmbH had been added in liquid form to deionized water before, with stirring.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Detergent Compositions (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (16)

  1. Utilisation d'un adjuvant de type silane pour éviter l'apparition de points sur des surfaces métalliques comportant du zinc,
    1) dans une composition aqueuse de nettoyage,
    2) dans un liquide aqueux de rinçage qui est utilisé
    a) avant un nettoyage,
    b) entre plusieurs zones de nettoyage,
    c) immédiatement après un nettoyage,
    d) et/ou comme liquide réfrigérant,
    3) et/ou dans une composition aqueuse d'activation,
    étant entendu que la teneur en respectivement au moins un silane, silanol et/ou siloxane d'au moins l'une de ces compositions aqueuses, calculée par rapport au silane respectif, se situe dans l'intervalle allant de 0,001 à 5 g/L.
  2. Utilisation d'un adjuvant de type silane, conforme à la revendication 1,
    1) dans un bain aqueux de nettoyage,
    2) dans un bain aqueux de rinçage dont le liquide est utilisé
    a) avant un nettoyage,
    b) entre plusieurs zones de nettoyage,
    c) immédiatement après un nettoyage,
    d) et/ou aux fins de réfrigération,
    3) et/ou dans un bain aqueux d'activation,
    étant entendu que la teneur en respectivement au moins un silane, silanol et/ou siloxane d'au moins l'un de ces bains aqueux, calculée par rapport au silane respectif, se situe dans l'intervalle allant de 0,001 à 5 g/L.
  3. Utilisation d'un adjuvant de type silane, conforme à la revendication 1 ou 2,
    1) dans la composition aqueuse de nettoyage d'une zone de nettoyage,
    2) dans le liquide aqueux de rinçage d'une zone de rinçage dont le liquide est utilisé
    a) avant un nettoyage,
    b) entre plusieurs zones de nettoyage,
    c) immédiatement après un nettoyage,
    d) et/ou aux fins de réfrigération,
    3) et/ou dans la composition aqueuse d'activation d'une zone d'activation d'une ligne de traitement,
    étant entendu que la teneur en silane dans au moins l'une de ces zones, calculée par rapport au silane respectif, se situe dans l'intervalle allant de 0,001 à 5 g/L.
  4. Utilisation d'un adjuvant de type silane, conforme à l'une au moins des revendications 1 à 3, dans au moins une composition aqueuse d'un bain ou d'une zone
    A) pour nettoyage, rinçage et/ou activation avant une phosphatation,
    B) ou pour nettoyage et/ou rinçage avant une passivation ou un pré-traitement avec une composition aqueuse de conversion contenant des ions fluorure et/ou des ions complexes titanifluorure, hafni-fluorure et/ou zirconifluorure, un silane, des cations de métaux tels que du manganèse, un polymère/copolymère organique et/ou au moins un adjuvant,
    C) ou située avant une passivation en milieu aqueux alcalin, neutre ou acide réalisée avec une composition contenant des cations de métaux, des ions fluorures complexes, un oxyde, un phosphate, un silane, un silicate, un polymère/copolymère organique et/ou au moins un adjuvant.
  5. Utilisation d'un adjuvant de type silane, conforme à l'une au moins des revendications 1 à 4, dans au moins une composition aqueuse d'un bain ou d'une zone situé(e) avant une phosphatation alcaline, avant une phosphatation au manganèse ou avant une phosphatation au zinc.
  6. Utilisation d'un adjuvant de type silane, conforme à l'une au moins des revendications 1 à 5, dans une composition aqueuse d'activation (A) à base de particules de phosphates de métal ou de métaux divalent(s) et/ou trivalent(s) présentant une taille moyenne de particule valant jusqu'à 3 µm et d'au moins une autre substance choisie parmi les agents dispersants, les agents épaississants, les tensioactifs et les adjuvants tels que par exemple les biocides.
  7. Utilisation d'un adjuvant de type silane, conforme à l'une au moins des revendications 1 à 6, dans une composition aqueuse d'activation (B) à base de 0,001 à 10 g/L de phosphate de titane, en particulier colloïdal, de 0,005 à 30 g/L d'orthophosphate dissous dans l'eau et d'au moins une autre substance choisie parmi les phosphates condendensés, les tensioactifs, les agents stabilisants, les agents épaississants et les biocides.
  8. Utilisation d'un adjuvant de type silane, conforme à l'une au moins des revendications 1 à 7, dans un liquide aqueux de rinçage dont le pH vaut de 3 à 14.
  9. Utilisation d'un adjuvant de type silane, conforme à l'une au moins des revendications 1 à 8, dans une composition aqueuse de nettoyage contenant des ions de métaux lourds, comme par exemple des ions de fer, et un agent complexant, ou dans une composition aqueuse de nettoyage et/ou un liquide aqueux de rinçage utilisé(s) avant un traitement par une composition aqueuse de passivation, contenant un agent complexant et des ions de métal, comme par exemple d'aluminium, et/ou des ions de métaux lourds comme par exemple de chrome-III, de fer, de manganèse et/ou de zinc.
  10. Utilisation d'un adjuvant de type silane, conforme à l'une au moins des revendications 1 à 9, dans une composition aqueuse de nettoyage dont le pH vaut de 3 à 14, dont la teneur totale en tensioactifs vaut de 0,01 à 10 g/L et qui contient au moins un tensioactif non-ionique.
  11. Utilisation d'un adjuvant de type silane, conforme à l'une au moins des revendications 1 à 10, étant entendu que lors de la préparation d'une composition aqueuse contenant un silane, c'est chaque fois au moins un silane, un silanol et/ou un siloxane comportant au moins un groupe alcoxy, au moins un groupe amido, au moins un groupe amino, au moins un groupe urée et/ou au moins un groupe imino par molécule qui est/sont ajouté(s) et qui est/sont ensuite contenu(s) dans la composition aqueuse contenant un silane.
  12. Utilisation d'un adjuvant de type silane, conforme à l'une au moins des revendications 1 à 11, étant entendu que lors de la préparation d'une composition aqueuse contenant un silane, c'est à chaque fois au moins un silane, un silanol et/ou un siloxane comportant au moins deux groupes amino, au moins trois groupes amino, au moins quatre groupes amino, au moins cinq groupes amino et/ou au moins six groupes amino par molécule et/ou au moins deux, au moins trois ou plus de trois groupes alcoxy par molécule qui est/sont ajouté(s) et qui est/sont ensuite contenu(s) dans la composition aqueuse contenant un silane correspondante.
  13. Utilisation d'un adjuvant de type silane, conforme à l'une au moins des revendications 1 à 12, étant entendu que lors de la préparation d'une composition aqueuse contenant un silane, c'est à chaque fois au moins un alcoxy-silane, un alcoxy-silanol et/ou un alcoxy-siloxane comportant au moins un groupe amido, au moins un ou au moins deux groupe(s) amino, au moins un groupe urée et/ou au moins un groupe imino par molécule qui est/sont ajouté(s) et qui est/sont ensuite contenu(s) dans la composition aqueuse contenant un silane correspondante.
  14. Utilisation d'un adjuvant de type silane, conforme à l'une au moins des revendications 1 à 12, étant entendu que lors de la préparation d'une composition aqueuse contenant un silane, c'est à chaque fois au moins un alcoxy-silane, un alcoxy-silanol et/ou un alcoxy-siloxane comportant deux, trois ou plus de trois groupes amino par molécule qui est/sont ajouté(s) et qui est/sont ensuite contenu(s) dans la composition aqueuse contenant un silane correspondante.
  15. Utilisation d'un adjuvant de type silane, conforme à l'une au moins des revendications 1 à 14, étant entendu que lors de la préparation d'une composition aqueuse contenant un silane, c'est à chaque fois au moins un silane, un silanol et/ou un siloxane choisi(s) parmi les composés de type silane de la liste suivante qui est/sont ajouté(s) en une concentration de 0,001 à 5 g/L, calculée par rapport au silane respectif, et qui est/sont ensuite contenu(s) en une concentration de 0,001 à 5 g/L, calculée par rapport au silane respectif, dans la composition aqueuse contenant un silane :
    - 3-[2-(2-amino-alkyl)-amino-alkyl]-amino-alkyl-trialcoxy-silane,
    - (4-amino-dialkyl-alkyl)-trialcoxy-silane,
    - (4-amino-dialkyl-alkyl)-alkyl-dialcoxy-silane,
    - (amino-alkyl-amino-alkyl)-trialcoxy-silane,
    - (amino-alkyl-amino-alkyl)-alkyl-dialcoxy-silane,
    - (amino-alkyl)-trialcoxy-silane,
    - bis(trialcoxy-silyl-alkyl)-aminé,
    - bis(trialcoxy-silyl)-éthane,
    - (γ-amino-alkyl)-trialcoxy-silane,
    - [γ-(trialcoxy-silyl)-alkyl]-dialkylènetriamine,
    - (γ-uréido-alkyl)-trialcoxy-silane, [N-(2-amino-alkyl)-3-amino-propyl]-trialcoxy-silane,
    - N-[3-(trialcoxy-silyl)-alkyl]-alkylènediamine,
    - [(N-alkyl-amino)-isoalkyl]-trialcoxy-silane,
    - [(N-amino-alkyl)-amino-alkyl]-alkyl-dialcoxy-silane,
    - [N-(β-amino-alkyl)-γ-amino-alkyl]-trialcoxy-silane,
    - N-[γ-(trialcoxy-silyl)-alkyl]-dialkylènetriamine, et/ou
    - poly(amino-alkyl)-alkyl-dialcoxy-silane,
    étant entendu que les groupes « alkyl » sont, indépendamment les uns des autres, des groupes méthyle, éthyle et/ou propyle.
  16. Utilisation d'un adjuvant de type silane, conforme à l'une au moins des revendications 1 à 15, étant entendu que lors de la préparation d'une composition aqueuse contenant un silane, c'est à chaque fois au moins un silane, un silanol et/ou un siloxane choisi(s) parmi les composés de type silane à base de bis(trialcoxy-silyl-propyl)-amine, à base de N-[3-(trialcoxy-silyl)-propyl]-éthylènediamine et/ou à base de 3-[2-(2-amino-alkyl)-amino-alkyl]-amino-propyl-trialcoxy-silane qui est/sont ajouté(s) et qui est/sont ensuite contenu(s) dans la composition aqueuse contenant un silane correspondante.
EP14703815.2A 2013-02-13 2014-02-07 Procédé permettant le revêtement de surfaces métalliques pour éviter la formation de piqûres sur des surfaces métalliques contenant du zinc Active EP2956569B1 (fr)

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DE102013202286.7A DE102013202286B3 (de) 2013-02-13 2013-02-13 Verwendung eines Silan-, Silanol- oder/und Siloxan-Zusatzes zur Vermeidung von Stippen auf Zink-haltigen Metalloberflächen und Verwendung der beschichteten Metallsubstrate
PCT/EP2014/052383 WO2014124866A1 (fr) 2013-02-13 2014-02-07 Procédé permettant le revêtement de surfaces métalliques pour éviter la formation de piqûres sur des surfaces métalliques contenant du zinc

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EP2956569A1 EP2956569A1 (fr) 2015-12-23
EP2956569B1 true EP2956569B1 (fr) 2017-04-12

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US (1) US20150361382A1 (fr)
EP (1) EP2956569B1 (fr)
JP (2) JP6405321B2 (fr)
KR (2) KR20150119241A (fr)
CN (1) CN105324516B (fr)
BR (1) BR112015019215B1 (fr)
DE (1) DE102013202286B3 (fr)
ES (1) ES2632616T3 (fr)
MX (1) MX2015010440A (fr)
PL (1) PL2956569T3 (fr)
RU (1) RU2680040C2 (fr)
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ZA (1) ZA201506777B (fr)

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WO2015124322A1 (fr) * 2014-02-20 2015-08-27 Tata Steel Ijmuiden B.V. Traitement d'activation de substrats d'acier revêtus
CN104403389A (zh) * 2014-11-24 2015-03-11 青岛市市南区隆德中医药研究所 一种不易出现针孔的油漆

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3541997A1 (de) * 1985-11-28 1987-06-04 Collardin Gmbh Gerhard Verbessertes verfahren zur aktivierung von metalloberflaechen vor einer zinkphosphatierung
DE3635343A1 (de) * 1986-10-17 1988-04-28 Metallgesellschaft Ag Verfahren zur erzeugung von phosphatueberzuegen
DE3731049A1 (de) 1987-09-16 1989-03-30 Henkel Kgaa Verfahren zur herstellung von aktivierenden titanphosphaten fuer die zinkphosphatierung
DE4012795A1 (de) 1990-04-21 1991-10-24 Metallgesellschaft Ag Aktivierungsmittel fuer die phosphatierung
US5292549A (en) * 1992-10-23 1994-03-08 Armco Inc. Metallic coated steel having a siloxane film providing temporary corrosion protection and method therefor
US6162547A (en) * 1998-06-24 2000-12-19 The University Of Cinncinnati Corrosion prevention of metals using bis-functional polysulfur silanes
US6827981B2 (en) * 1999-07-19 2004-12-07 The University Of Cincinnati Silane coatings for metal
US6652977B2 (en) * 2001-09-10 2003-11-25 Johnson Diversey, Inc. Primer composition
ES2364405T3 (es) 2004-02-20 2011-09-01 Chemetall Gmbh Acondicionador de superficie y método de acondicionamiento de superficie.
EP1825022B1 (fr) * 2004-11-10 2019-04-17 Chemetall GmbH Procédé de production d'un revêtement de réparation sur une surface métallique revêtue
US7695771B2 (en) * 2005-04-14 2010-04-13 Chemetall Gmbh Process for forming a well visible non-chromate conversion coating for magnesium and magnesium alloys
US8119239B2 (en) * 2005-08-19 2012-02-21 Nippon Paint Co., Ltd. Surface-conditioning composition comprising metal phosphate particles, metal alkoxide and stabilizer, and method of production thereof
US20080283152A1 (en) * 2007-05-17 2008-11-20 Jeffrey Allen Greene Rinse conditioner bath for treating a substrate and associated method
DE102008054407B4 (de) * 2008-12-09 2018-03-29 Chemetall Gmbh Verfahren zur Beschichtung von metallischen Oberflächen mit einem Aktivierungsmittel vor dem Phosphatieren, entsprechende Aktivierungsmittel sowie Verwendung der mit dem Verfahren beschichteten Substrate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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BR112015019215A2 (pt) 2017-07-18
MX2015010440A (es) 2016-02-09
JP2019007089A (ja) 2019-01-17
RU2680040C2 (ru) 2019-02-14
US20150361382A1 (en) 2015-12-17
BR112015019215B1 (pt) 2021-08-03
JP2016514203A (ja) 2016-05-19
EP2956569A1 (fr) 2015-12-23
PL2956569T3 (pl) 2017-09-29
JP6405321B2 (ja) 2018-10-17
KR20210057218A (ko) 2021-05-20
DE102013202286B3 (de) 2014-01-30
KR102301323B1 (ko) 2021-09-14
ZA201506777B (en) 2017-01-25
WO2014124866A1 (fr) 2014-08-21
RU2015138786A (ru) 2017-03-20
ES2632616T3 (es) 2017-09-14
CN105324516A (zh) 2016-02-10
KR20150119241A (ko) 2015-10-23
CN105324516B (zh) 2018-08-10

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